Novel triazino-benzimidazoles

ABSTRACT

Triazino-benzimidazoies of the formula   IN WHICH R is a variety of substituents including alkyl, cycloalkyl, bi- and tricycloalkyl, phenyl and phenalkyl, are valuable fungicides.

United States Patent Riichling et al.

[451 July 22,1975

NOVEL TRlAZlNO-BENZIMIDAZOLES Inventors: Hans R'dchling, Altenhain, Taunus;

Kurt Hiirtel, Hofheim, Taunus, both of Germany Hoechst Aktiengesellschaft, Frankfurt am Main, Germany Filed: May 14, 1973 Appl. No: 361,073

Assignee:

Foreign Application Priority Data May 18, 1972 Germany .1 2224244 Feb. 13, 1973 Germany 2308067 References Cited UNITED STATES PATENTS 7/1948 Heimbach et al 260/2495 X OTHER PUBLICATIONS Smolin et al., S-Triazines and Derivatives, pages 428 to 432, Interscience Publishers, Inc. NY (1959).

Primary Examiner-John D. Randolph Attorney, Agent, or F [rm-Curtis, Morris & Safford [57] ABSTRACT Triazino-benzimidazoies of the formula in which R is a variety of substituents including alkyl, cycloalkyl, biand tricycloalkyl, phenyl and phenalkyl, are valuable fungicides.

18 Claims, No Drawings Schlapfer et a1. 260/2496 t 1 NOVEL TRIAZlNO-BENZIMIDAZOLES The present invention relates to triazinobenzimidazoles of the formula I coocn where R is alkyl having from 1 to 18 carbon atoms; alkenyl having from 3 to 18 carbon atoms, alkinyl having from 2 to 8 carbon atoms, cycloalkyl having from 3 to 12 carbon atoms, optionally substituted by one or more alkyl groups having from l to 4 carbon atoms or by hydroxy; cyclohexylalkyl, cyclohexylalkenyl, or cyclohexylalkinyl each having from 1 to 3 carbon atoms in the chain, endomethylene-cyclohexylmethyl, endomethylenecyclohexenylmethyl, tricyclodecyl, or tricyclodecenyl; phenalkyl, diphenylalkyl or triphenylalkyl each having from 1 to 6 carbon atoms in the alkylene radical, the phenyl nuclei of which being optionally substituted by halogen, alkyl, alkoxy, alkylthio each having from 1 to 4 carbon atoms, or di- (C -C )-amino;

phenyl or naphthyl, optionally being substituted each by alkyl having from 1 to 4 carbon atoms, halogen, halogeno-alkyl having from 1 to 4 carbon atoms, trifluoromethyl, hydroxy, alkoxy having from 1 to 4 carbon atoms, phenoxy or (C -C )-alkylthio; di- (C,C )-alkyl-amino-(C -C )-alkyl; hydroxy(C- -C )-alkyl, (C -C )-alkoxyalkyl or dialkoxyalkyl, (C -C )-alkylmercaptpalkyl, (C -C )-dialkylphosphinylalkyl, furfuryl-alkyl, morpholino-(C -C alkyl pyrrolidino-(C -C )-alkyl, piperidino- (C C )-alkyl or (C -C )-carbalkoxylalkyl.

The present invention relates furthermore to a process for the preparation of compounds of formula I, which comprises reacting 2-methoxycarbonylaminobenzimidazole of the formula II NH-COOCH 3 with a primary amine of the formula H NR (Ill) and formaldehyde.

A preferred embodiment of the process of the present invention" is the following: The Z-methoxycarbonylamino-benzimidazole (II) is suspended or dissolved in a solvent, the molar to twice molar amount of the amine is added and subsequently, with agitation, the two to four times molar amount of an aqueous for maldehyde solution is added. The operational temperature is advantageously kept at to 80C, especially 20 to 40C, but the temperature range is not critical. The reaction product normally dissolves and may be separated by filtering the solution from a Z-methoxycarbonylamine-benzimidazole residue; concentration of the solution and treatment with an inert solvent, such as gasoline, or reprecipitation, for example from methylene chloride/gasoline, yields zimidazole in pure form.

The reaction always proceeds with formation of the final product I, even when there is a deficiency of formaldehyde.

Preferred amines of formula ill for the reaction are those in which R is straight-chain or branched alkyl having from 1 to 15 carbon atoms; alkenyl having from 3 to 18 carbon atoms; cycloalkyl having from 3 to 12 carbon atoms, which may be substituted by alkyl having from 1 to 4 carbon atoms, especially by methyl or ethyl; tricyclodecyl, phenyl or naphthyl; phenyl or naphthyl monoor di-substituted by methyl, ethyl, tert.-butyl, chlorine or hydroxy; phenylalkyl having from 7 to 9 carbon atoms, especially benzyl, or diphenylalkyl having from 13 to 14 carbon atoms the phenyl groups 'of which may be substituted by chlorine or methyl; alkoxy-alkyl, dialkoxyalkyl or alkylmercaptoalkyl having from 3 to 8, especially from 3 to 4 carbon atoms; hydroxyalkyl having from 3 to 7, especially from 3 to 6 carbon atoms; dialkyl-phosphinylalkyl having from 3 to 9, especially from 3 to 5 carbon atoms; morpholino-alkyl having from 5 to 8, especially from 6 to 7 carbon atoms, or carbalkoxy having from 3 to 12, especially from 4 to 8 carbon atoms.

Besides the amines used in the examples, the following amines may therefore be used:

iso-amylamine, iso-octylamine, nonylamine, ndecylamine, isodecylamine, n-undecylamine, pentadecylamine, hexadecylamine, octadecylamine, n-octadecen-9-ylamine, cyclobutylamine, 2-methylcy+ clopentylamine, N,N-dimethyl-, N,N-diethyl, N,N- dibutyl, N,N-methylethyl-, N-methyl-N-propyl-, N- ethyl-N-isobutylethylene-diamine or the corresponding propylenediamines, tetramethylene-diamines and hexamethylene-diamines, 3-aminohexahydro-toluene, 4-amino-hexahydro-m-xylene, 4-isopropylcyclohexylamine, 4-ethyl-cyclohe'.'ylamine, 2,6-diethylaniline, 4- tert.-butylamiline, 2-, 3- and 4-chloroaniline, 2-, 3- and the triazinoben- 4-aminophenol, aand B-naphthylamine, 3- phenylpropylamine, 2-phenylethylamine, 4-phenylbutylamine, diphenylmethylamine, 2,2-

diphenylethylamine, 2-, 3- and 4-chlorobenzylamine, 2-(2-chlorophenyl)-ethylamine, 2-, 3- and 4- methylbenzylamine, 2-ethylthio-ethylamine, 4- methylthio-butylamine, land 4-amino-hexanol, dimethyl-(2-amino-ethyl)-phosphine oxide, diethyl(4- aminobutyl)-phosphine oxide, N-aminomethylmorpholine, N-(3-aminopropyl)-morpholine, N-aminoethyl-pyrrolidine, N-aminomethyland N-aminoethyLpiperidine, furfurylamine, aminoacetic acid methyland -ethyl ester, 2-aminoproprionic acid methyl ester, 3-aminobutyric acid ethyl ester, 6- aminocapronic acid methyland -ethyl ester, alanine methyl ester, 'y-aminovaleric acid methyland -ethyl ester, 4-methoxybenzylamine, 4-tert.-butylcyclohexylamine, 2-amino-l ,3 ,S-trimethylbenzene, 2- aminobutane, 2-e thylhexylamine, n-tridecylamine and tetradecylamine, or iso-tetradecylamine.

Suitable solvents for the reaction are above all mod erately or weakly polar solvents, preferably those having a low boiling point, for example methylene chloride, chloroform, carbon tetrachloride, benzene; ethers such as diethyl ether, di-isopropyl ether or tetrahydrofuran; esters such as methyl acetate or ethyl acetate; or ketones such as acetone or methylethyl ketone. Preferably, chloroform or methylene chloride are used.

The 2-methoxycarbonylamine-benzimidazole may be prepared according to the method described in J. Am. Chem. Soc. 56, 144 (1934), by reaction of O-phenylene-diamine with S-methyl-isothiourea dicarboxylic acid dimethyl ester. The preparation of the amines required for the reaction is also known from the literature.

The compounds of the invention have an excellent fungicidal, especially systemic, action, so that they can be used for combating fungus germs having already intruded into the plant tissue in a curative manner. This is especially important in the case of those fungus diseases which have a long incubation period and, after the outbreak of the infection, cannot be combated any more by the usual fungicides. The activity range of these compounds is very broad and includes a series of fungus germs important in crop farming, fruit growing, viticulture, hop growing, or horticulture, as for example Fusicladium Spp, Gloeosporium Spp, Cylindrosporium Spp, Botrytis Spp, Verticillium Spp, Cercospora Spp, Septoria Spp, Mycosphaerella Spp, Cladosporium Spp, Colletotrichum Spp, Rhizoctonia Spp, Fusarium Spp, Cercosporella Spp, ustilagineae, erysiphaceae, aspergillaceae or sclerotinaceae.

Furthermore, a number of the compounds of the invention, especially those having long-chain radicals, have an excellent activity against phycomycetes, such as the Peronospora or Phytophthora species. Their degree of efficiency in this particular respect is equal to that of the metal salts of dithiocarbamic acid or the N- trichloromethylthio-phthalimide derivatives, and in many cases is even superior to them.

The compounds of the invention may also be used for protecting stored fruits or vegetables against fungus infection (for example species of Fusarium or Penicillium and the like.)

Furthermore, they are suitable for technological application, for example for protecting textiles, wood, dyes or coatings against infection with rot and other fungus germs.

The present invention therefore relates to pesticides, especially fungicides, containing the triazinobenzimidazoles of formula I as active substance, especially in concentrations of from 2 to 95 in combination with usual formulation additives such as solid or liquid inert carriers, adhesives, wetting and dispersing agents and/or grinding auxiliaries in the form of wettable powders, emulsions, suspensions, dusting powders or granules. They may be mixed with other fungicides with which they form compatible mixtures.

As carrier material, mineral substances, for example aluminium silicates, argillaceous earths, kaolin, chalks, siliceous chalks, talcum, kieselguhr or hydrated silicic acids can be used, or preparations of these mineral substances with special additives, for example chalk with sodium stearate. As carrier material for liquid preparations, all usual and suitable organic solvents may be employed, for example toluene, xylene, diacetone alcohol, isophorone, gasolines, paraffin oils, dioxan, dimethyl formamide, dimethyl sulfoxide, ethyl acetate, tetrahydrofuran, chlorobenzene, and the like.

Suitable adhesives are glue-like cellulose products or polyvinyl alcohols.

As wetting agents, all suitable emulsifiers may be used, for example ethoxylated alkylphenols, salts of arylor alkylaryl-sulfonic acids, salts of oleyl-methyltaurine or of ethoxylated benzenesulfonic acids, or

soaps.

Suitable dispersing agents are cellulose pitch (salts of ligninsulfonic acid, salts of naphthalenesulfonic acid or salts of oleyl-methyl-taurine.

As grinding auxiliaries, suitable inorganic or organic salts, for example sodium sulfate, ammonium sulfate, sodium carbonate and sodium bicarbonate, sodium thiosulfate, sodium stearate, or sodium acetate may be used.

Furthermore, the compounds of formula I have an anthelmintic activity in the veterinary field and may therefore be used for combating dificrent worm diseases in domestic animals and productive livestock The following examples of preparation and application illustrate the invention.

A. EXAMPLES OF PREPARATION EXAMPLE 1 57.3 g (0.3 mole) of 2-methoxycarbonylaminobenzimidazole were suspended in 550 ml of methylene chloride, 55.5 g (0.3 mole) of dodecylamine were added and the whole was heated to 35C. At this temperature, 68 ml (0.8 mole) of aqueous 35 formaldehyde solution were added dropwise with agitation, which was continued subsequently for 1 hour at 38C, before the mixture was allowed to cool, also with agitation.

The non-converted 2-methoxycarbonylaminobenzimidazole was suction-filtered, the aqueous layer was separated and the methylene chloride solution was dryed over magnesium sulfate and concentrated, yielding 122.7 g of a crystalline substance having a melting point of C.

In order to eliminate adhering amine, this substance was stirred with 200 ml of gasoline (30/85C); thus obtaining g (79 of the theoretical yield) of lmethoxycarbonyl-3-dodecyl-s-hexahydrotriazinobenzimidazole having a melting point of 86 to 87C.

cooca,

molecular weight: 4-00 calc: C 69.0 H 9. found: C 69.3 H 9.

In the infrared spectrum, the compound had a characeteristic carbonyl absorption at 1720 cm", as well as double bond bands at 1620 cm and 1595 cm".

EXAMPLE la 57.3 g (0.3 mole) of Z-methoxycarbonylaminobenzimidazole were suspended in 900 ml of methylene chloride, and 39 g (0.3 mole) of 3-diethylamino-lpropylamine were added: The suspension was heated to 35C. At this temperature; 60ml"( 0.7 m0le)-of 35 formaldehyde solution were added dropwise with agitation, which was then continued at 38C for 2 hours, be-

fore the mixture was allowed vto cool, alsov with agitation. The non-converted 2-methoxycarbonylaminobenzimidazole was suction-filtered, the aqueous layer was separated, and the methylene chloridesolution was dried over magnesium sulfate and concentrated, yielding an oily residue which was stirred at 30' to 85C with gasoline. After decanting, the gasoline solution was concentrated, the oily residue obtained was redissolved in methylene chloride and washed twice with water. The methylene chloride solution was then dried over MgSO concentrated, and the oily residue was degassed at room temperature under highly reduced pressure.

Yield: 37 g (36 of the theoretical yield) of a nondistillable oil.

coocii c H mo MW: 345 calc.: C 62.6 H 7.8 N 20.2 found: C 63.0 H 8.5 N 19.8

EXAMPLE 2 38.2 g (0.2 mole) of 2-methoxycarbonylaminobenzimidazole were suspended in 600 ml of chloroform, 14.6 g (0.2 mole) of n-butylamine were added, and the whole was heated to 35C. At this temperature, 68 ml.(0.8 mole) of 35 aqueous formaldehyde solution was added dropwise, with agitation, which was then continued at 38C for 1 hour. The benzimidazole dissolved while reacting. The mixture was allowed to cool, the aqueous layer was eliminated,"and the organic phase was dried over magnesium sulfate.

After filtration and concentration, an oil was obtained which solidified after trituration with n-hexane.

Yield: 41 g (71 of the theoretical yield) of 1- methoxy-3-n-butyl-s-hexahydro-triazinobenzimidazole; melting point 109C.

eooc i, C I NW \/N\ CAHQ 2O 4 z MW 288 calc.: c 62.5 H 6.94 N 19.45% found: c 62.8 H I 7.2 N 19.5

In the infrared spectrum, the compound showed a l carbonyl absorption at 1745 cm, and double bond bands at 1620 cm".

benzimidazole were suspended in 900 ml of methylene chloride, 26.7 g (0.3 mole) of 3-rnethoxy-propylamine were added and the whole was heated to 35C. At this temperature, 68 ml (0.8 mole) of aqueous 35 formaldehyde solution were added dropwise, with agitation, which was subsequently continued at 38C for 1 hour.

After cooling, the mixture was filtered off a small amount of non-converted starting benzimidazole. The aqueous phase was separated, and the methylene chloride solution was dried over magnesium sulfate.

After filtration and concentration, an oil was obtained which solidifies on trituration with n-hexane. Yield: 63 g (69 of the theoretical yield) of 1- methoxycarbonyl-3-(3'-methoxypropy1)-s-hexahydrotriazino-benzimidazole.

Melting point: 73 to 74C.

In the infrared spectrum, the. compound showed a carbonyl absorption at 1750 crrffand double bond bands at 1625 cm and 1600 cm. The substances of the formula as indicated in the following Table are prepared ac- B. EXAMPLES OEAPPLICATION EXAMPLEI Cucumber plants were grown in pots, and in the 2- leaf stage treated, until drip-off, with aqueous suspensions of the compounds of Examples 1, 2 and 4 to 15. Before the treatment, newly grown leaves of the plants and the soil were carefully covered with plastic sheets in such a manner that they were not touched by the spray liquor.

The application concentrations were 2000, 1000, 500, 250 and 125 mg of active substance per liter of spray liquor. As comparative agent, benomyl (l-N butyl-carbamoyl-Z-methoxycarbonylaminobenzimidazole) was used.

After drying of the sprayed layer, the protective sheets were removed and the plants placed in a greenhouse. When the 4th and 5th leaves had developed, the plants were heavily infested with conidia of cumcumber mildew (Erysiphe cichoracearui'n) andsubsequently placed in a moisture chamber at a temperature of 22C and a relative atmospheric humidity of 100 After a residence time of 24 hours, the plants were transferred to a greenhouse having a high relative atmospheric humidity (80 to 90 and a temperature of from 22 to 23C, where they were kept until the outbreak of the disease.

The evaluation of the infection was carried out visibly, as usual, and the infection degree is expressed in of infested leaf area as compared to untreated, infested control plants. The results are shown in Table I.

EXAMPLE 11 Garden earth was mixed in a shaking machine for minutes with the compounds of the invention cited in Example I in application amounts of 10, 5, 2.5, 1.25, 0.6 and 0.3 mg of active substance/kg of earth. As comparative agent, benomyl was used in the same application amounts as the preparations of the invention.

Pots were charged with the earth so treated and 10 grains each of winter wheat of the of the brand Heine VII were sown, before the pots were placed in a greenhouse having a high atmospheric humidity and a temperature of 22C for germination. After emergence of the wheat, the plants, in the 4- to 5-leaf stage, were heavily infested with conidia of the powdery mildew of cereals (Erysiphe graminis). After an incubation period of 14 days, the plants were visibly examined for infection with mildew. The degree of infection was expressed in of infested leaf area as compared to untreated, infested control plants. The results are indicated in Table II.

EXAMPLE III Sugar beet plants in the 6-leaf stage were heavily infested with conidia of the beet leaf spot organism (Cercospora beticola) and placed dripping wet in a moisture chamber at 25C and a 100 relative atmospheric humidity, where they were kept for 24 hours. Subsequently, they were placed in a greenhouse having a relative atmospheric humidity of from 85 to 90 and a temperature of from 24 to 25C. After an infection time of 7 days, the plants were sprayed, until drip-off, with aqueous suspensions of the compounds cited in Example I.

The application concentrations were 60, 3O, and 7.5 mg/] of spray liquor. As comparative agent, benomyl was used in the same application concentrations.

After drying of the spray liquor, the plants were placed again in the greenhouse. After an incubation period of 3 weeks, the plants were examined for infection with beet leaf spot. The evaluation was carried out visibly, and the degree of infection expressed in of infested leaf area, as compared to untreated, infested control plants. The results are shown in Table III.

EXAMPLE IV Tomato plants, in the stage of completely grown 3 leaves, were heavily infested with conidia of the leaf mould of tomatoes (Cladosporium fulvum), and placed dripping wet for one day in a moisture chamber having a temperature of 25C and a relative atmospheric humidity of 100 They were then transferred to a greenhouse having a relative atmospheric humidity of from to and a temperature of from 23 to 25C. After 7 days, the plants were treated with aqueous suspensions of the compounds according to Examples 16 to 24 in concentrations of 60, 3O, 15 and 7.5 mg/l of spray liquor. As comparative agent, benomyl was used.

After drying of the sprayed layer, the plants were again placed in the greenhouse and, after an incubation period of 21 days, examined for infection with leaf mould. The infection was examined visibly, as usual, and the degree of infection was expressed in of infested leaf area relative to untreated, infested control plants.

The results are shown in Table IV.

EXAMPLE V Wheat plants were grown in pots and in the 2-leaf stage treated, until drip-off, with the compounds cited in Example IV. The application concentrations were 2000, 1000, 500, 250 and 125 mg/l of spray liquor. As comparative agent, benomyl was used in the same concentrations of active substance as cited.

After drying of the layer of spray liquor, the plants were placed in a greenhouse, where they were kept until the 4th and 5th leaves were fully developed. In this stage, the plants were heavily infested with conidia of the powdery mildew of cereals (Erysiphe graminis), the temperature of the greenhouse was adjusted to 22 to 23C, and the relative atmospheric humidity to 80 to 90 in order to create optimum infection conditions for the mildew.

After incubation period of 10 days, the plants were visibly examined for infection, and the degree of infection was expressed in of infested area, relative to untreated, infested control plants. The results are indicated in Table V.

EXAMPLE VI Winter wheat of the Heine VII brand was homogeneously seed-treated for 10 minutes in a shaking machine with the compounds cited in Example IV and benomyl, in application amounts of 200, I00, 50 and 25 g of active substance per kg of seeds.

Subsequently, 5 times 10 grains each of the treated seeds were sown in pots filled with earth, and placed in a greenhouse for germination.

When the 4th and 5th leaves of the plants had developed, the plants were heavily infested with conidia of the powdery mildew of cereals (Erysiphe graminis) and the greenhouse adjusted to a relative atmospheric huresults are shown inTable EXAMPLE VII Wheat plants of the Heine VII brand, in the 3-leaf stage, were infested with conidia of the powdery mildew of cereals (Erysiphe graminis) and, 3 days after the infection, treated with aqueous suspensions of the compounds according to Examples 3 and 25 to 32, until they were dripping wet. The application concentrations were 120, 60, 30 and 15 mg of active substance/l of spray liquor. As comparative agent, benomyl was used in the same application concentrations.

After drying of the sprayed layer the plants were placed in a greenhouse having a relative atmospheric humidity of from 80to 90 and a temperature of from 22 to 23C.

l Days after the treatment, the plants were visibly examined for infection with mildew. The degree of infection was expressed in of infested leaf area, relative to untreated, infested control plants. The results of the test are indicated in Table VII.

EXAMPLE VIII Cucumber plants in the 2-leaf stage were treated, until drip-off, with aqueous suspensions of the compounds cited in Example VII, in application concentrations of 2000, 1000, 500 and 250 mg of active substancell of spray liquor; newly grown leaves and the soil being carefully protected by plastics sheets in such a manner that they were not touched by the spray liquor. The comparative agent was again benomyl.

After drying of the sprayed layer, the plants were placed in a greenhouse and were kept there until they had developed the 4th leaf. In this stage, all plants, including untreated control plants, were heavily infested with conidia of the cucumber mildew (Erysiphe cicho racearum), and placed in a moisture chamber having a temperature of 22C and a relative atmospheric humidity of I00 After 24 hours, the plants were transferred to a greenhouse having a high relative atmospheric humidity and a temperature of from 22 to 23C. After an incubation period of days, the plants were examined visibly for infection with cucumber mildew. The degree of infection was expressed in of infested leaf area, relative to untreated, infested control plants. The results are shown in Table VIII.

EXAMPLE IX Rice plants in the 4-leaf stage were heavily infested with Piricularia oryzae and subsequently placed in a moisture chamber having a temperature of 25C and a relative atmospheric humidity of 100 After a residence time of 24 hours, the plants were transferred to a greenhouse having a relative atmospheric humidity of 85 to 90 and a temperature of 25 to 26C. 4 Days after the infection, the plants were treated with the compounds cited in Example VII in application concentrations of 60, 30, I5 and 7.5 mg of active substance/l of spray liquor. As comparative agent, benomyl was used in the same application concentrations as above.

After drying of the sprayed layer, the plants were again placed in the greenhouse and, after in incubation period of 14 days, visibly examined for infection with Piricularia oryzae. The degree of infection was expressed in of infested leaf area, as compared to untreated, infested control plants. The results are shown in Table IX.

EXAMPLE X Young vine plants of the Peronospora predisposed MullerThurgau brand, in the 4-leaf stage, were treated, until dripofi', with aqueous's'uspensions of the compounds of Examples 1 and 12 to 15. The application concentrations were 500, 250, 125 and 60 mg of active substance per liter of spray liquor. As comparative agents, benomyl (Comparative Agent I) and folpet (N- (trichloromethylthio )-phthalimide Comparative Agent II) were used in the same concentrations of active substance as cited above.

After drying of the sprayed layer, the plants were heavily infested with a zoo-sporangia suspension of Peronospora viticola and placed dripping wet in a moisture chamber at a temperature of 20C and a relative atmospheric humidity of I00 After 24 hours, the infested plants were transferred to a greenhouse having a temperature of 23C and an atmospheric humidity of from to 90 After an incubation period of 7 days, the plants, which had been wetted, were again placed in the moisture chamber overnight and thus the infection caused to appear. The evaluation of the infection was carried out visibly, and the degree of infection was expressed in of infested leaf area, as compared to untreated, infested control plants. The results are listed in Table X.

EXAMPLE XI Vine plants grown from cuttings of the Muller- Thurgau brand, were sprayed in the 4-leaf stage, until drip-off, with aqueous suspensions of the compounds cited in Example X. The application concentrations were 20, 10, 5 and 2.5 mg of active substance/l of spray liquor. As comparative agents, benomyl and folpet were used in the same concentrations of active substance as indicated above.

After drying of the sprayed layer, the plants were placed in a greenhouse having a relative atmospheric humidity of to and a temperature of 23 to 25C, and heavily infested with conidia of the powdery mildew of vine (Oidium tuckeri).

After an incubation period of 14 days, the plants were examined for infection with Oidium, and the degree of infection was expressed in of infested leaf area, as compared to untreated, infested control plants. The results are indicated in Table XI.

EXAMPLE XII Tomato plants of the brand called Rheinlands Ruhm were sprayed in the 3-leaf stage with aqueous suspensions of the compounds indicated in Example X until drip-off. The application concentrations were 500, 250, 120, and 60 mg of active substance/l of spray liquor. As comparative agents, benomyl (Comparative Agent I) and zineb (zinc-ethylene-bis-dithiocarbamate Comparative Agent II) were used.

After drying of the sprayed layer, the plants were heavily infested with a zoo-sporangia suspension of Phytophthora infestans and placed dripping wet for l day in a moisture chamber having a temperature of 15C and a relative atmospheric humidity of 100 Subsequently, they were transferred to a greenhouse having a temperature of 15C and a relative atmospheric humidity of 85 to 95 After an incubation time of 7 days, the plants were examined visibly for infection with Phytophthora, and the degree of infection was expressed in of infested leaf area, as compared to untreated, infested control plants. The results are indicated in Table XII.

EXAMPLE XIII Barley plants in the 3-leaf stage were treated, until drip-off, with aqueous suspensions of the compounds of with germs of the celery leaf spot (Septoria apii), and subsequently placed in a moisture chamber having a temperature of 25C and an atmospheric humidity of 100 The plants were kept there for 1 day and were then transferred to a greenhouse having a temperature of 25 to 26C and a relative humidity of 85 to 90 After an incubation time of 5 days, the plants were treated, until drip-off, with aqueous suspensions of the compounds indicated in Examples la, 49, 50 and 51 and the comparative agent benomyl in application concentrations of 125 and 60 mg of active substance per liter of spray liquor. After drying of the spray liquor, the plants were placed again in the greenhouse and, after an incubation period of 21 days, visibly examined for infection with the celery leaf spot. The degree of in- Examples 1a, 49, 50 and 51 in application concentra- 15 tions f 60 and mg f active substance per liter f fection was expressed in of infested leaf area, relatlve Spray liqucm AS comparative agent, the Commercial to untreated, mfested control plants (Table XIII). product benomyl was used.

After drying of the sprayed layer, the plants were in- EXAMPLE XV fested with conidia of Piricularia oryzae, and placed 20 dripping wet in a moisture chamber at 25C and a rela- Dwarf bush bean seeds of the brand called Andreas tive atmospheric humidity of 100 The plants were were well mixed for 10 minutes in a shaking machine kept there for 1 day and then transferred to a greenwith the compounds of Examples 1a, 49, 50 and 51 and house having a temperature of 25 to 26C and a relathe comparative agent benomyl, in application tive atmospheric humidity of 100 25 amounts of 100 and 50 g of active substance per 100 After an incubation period of 7 days, the plants were kg of seeds, and, the following day, sown in earth which visibly examined for infection with Piricularia, and the before had been infested with a very virulent culture of degree of infection was expressed in of infested leaf Rhizoctonia solani. Four times 100 beans each were area, relative to untreated, infested control plants. The sown in pots filled with this earth. results are shown in Table XIII. 30 Three weeks after emergence of the bean plants, the number of emerged plants was counted and the plants EXAMPLE XIV were exammed for mfectlon with Rhizoctoma. The re- Celery plants in the 6-leaf stage were heavily infested sults of this test are indicated in Table XIII.

Table 1 7c of leaf area infested with compound cucumber mildew at mg of active according to substance/liter of spray liquor Example 2000 1000 500 250 125 4 0 0 5 0 O 3 12 18 6 0 0 5 1O 16 7 0 O 5 l2 l8 8 0 0 5 10 15 9 0 0 3 10 18 10 0 0 5 12 15 2 O 0 5 l0 l5 1 l O O 3 8 12 12 0 0 0 5 10 13 O O 0 5 l0 1 O O O 5 l0 l4 0 O 5 1O 12 15 0 0 3 5 10 benomyl O 5 8 15 control plants (untreated) 100 100 100 100 100 Table 11 compound of leaf area infested with powdery mildew of cereals acc, to at mg of active substanc/kg of earth Example 10 .5 1.25 0.6 0.3

4 0 o 0 5 12 5 O O O 5 15 2O 6 0 0 0 5 12 2O 7 O O O 5 1O 2O 8 O O O 5 10 25 9 O O O 5 12 2O 2 0 0 0 5 10 20 1O 0 O 0 5 12 18 l l O O 0 5 10 15 12 0 O O 0 5 l2 l3 0 O 0 O 5 1O 1 0 0 0 0 3 10 14 0 0 0 3 5 12 15 O O O 5 8 l5 benomyl 0 3 5 1O 20 3 control plants (untreated) 100 100 100 100 100 Table vn of infestation with powdery mildew of cereals at mg of active substance/liter of spray liquor 120 60 compound acc. to Example 1 at mg of active substance/liter spray liquor 6O 7.5

Table 111 compound of leaf area infested with Cercos according to Example 30 Table Vlll of cucumber mildew infection at mg of active substance/ liter of spray liquor 2000 1000 500 31 32 benomyl control plants (untreated) compounds acc. to Example uor Table IV of leaf area infested with Cladosporium at mg of active substance/liter of spray liq 60 30 benomyl (untreated) compound acc. to Example l OOOOOOOOO W 27 28 29 30 3 l 32 benomyl control plants untreated 24 benomyl control plants Table V of infection with powdery mildew of cereals at mg of active substance/liter of spray liquor 2000 I000 500 compound acc. to Example control plants (untreated) l8 l5 15 12 15 l0 l2 28 l6 l7 l8 19 20 21 22 23 24 benomyl Table 1X of piricularia infection at mg of active substance/liter of spray liquor 6O compound acc. to Example Table VI of mildew infection after seeds treatment with g of active substance/ kg of seeds 200 I00 compound acc. to Example control plants (untreated) 32 benomyl l6 l7 l8 I9 20 21 22 23 24 benomyl (untreated) control plants I00 (untreated) control plants Table X compound of Peronospora infection at mg of active cyclohexylalkyl, cyclohexylalkenyl, or cyclohexylalkinyl each having from I to 3 carbon atoms in the chain, endomethylene-cyclohexylmethyl, endome- .t -sbtanc /l'trofs ra l'uor i i pg 500 u szsoe le r y lq thylenecyclohexenylmethyl, tricyclodecyl, trlcy 5 clodecenyl; phenalkyl,'d1phenylalkyl or triphenyl5 3 5 lalkyl each having from I to 6 carbon atoms in the :5 8 8 g 2 alkylene radical, the phenyl nuclei of which being I 0 0 0 3 optionally substituted by halogen, alkyl, alkoxy or 14 0 0 3 8 CA I loo 100 I00 100 alkylthio each having from 1 t0 4 carbon atoms or CA u o 3 s l0 10 y r o control plants phenyl or naphthyl, optionally being substituted by (mtremed) 100 100 100 100 alkyl having from I to 4 carbon atoms, halogen, halogeno-alkyl having from 1 to 4 carbon atoms, trifluoromethyl, hydroxy, alkoxy having from 1 to Table XI 15 4 carbon atoms phenoxy or (C C )-alkylthio; di- (C -C,)-alkyl-amino-(C C )-alkyl; hydroxy(C- compound of O idium infection of the vine at mg of c y lk l (CTC1B lk lk or di lk l Eicacrhgfe active substance/liter of gpray liquor y r ls) y p y (C3 C9) dialkylphosphinylalkyl, furfuryl, morpholino l; 8 8 g 20 1- 4)- y pyrr0lidino-(C -C,,) alkyl, piperidi- 13 0 0' 0 s no-(C C )-alkyI or (C -C )-carbalkoxylalkyl. l 8 8 g 2. A compound as claimed in claim 1, having the for- CA I -'0 8 I5 23 "11113 CA II 65 80 I00 100 control plants 5 COOCHB (untreated) I00 I00 I00 I00 N a] Table XII (ca CH;,

compound of Phytophthora infection at mg of active A compound as Claimed in claim in which R has acc. to substance/liter of s ray liquor the formula Example 500 250 20 15 0 0 5 13 12. o 0 5 1g 2 a-Q l3 0 0 5 1 0 0 3 5 Q l4 0 3 5 IO CA I I00 I00 I00 100 CA II 0 3 5 l2 ont ol lants cmnrtreapted) I00 I00 I00 100 4. A compound aslclalmed in claim 1, m which R has the formula 40 Table XIII compound of infested leaf area of Rhizoctonia infested acc. to with Piricularia with Septoria plants at g of active substance/ Example at mg of active subst./l. of spray liquor 100 kg of seeds Example 60 30 125 60 100 la 0 8 O 8 0 8 49 0 5 0 3 0 8 50 0 5 0 5 0 5 5l 0 I2 0 8 0 l0 comp. agent benomyl 0 l0 0 5 0 l0 untreated infested I00 I00 I00 100 I00 I00 plants What is claimed is: --Cl-I -CI-ICH; l. A triazino-benzimidazoles of the formula cgooci-i R is alkyl having from 1 to 18 carbon atoms; alkenyl having from 3 to I8 carbon atoms, alkinyl having from 2 to 8 carbon atoms, cycloalkyl having from 3 to 12 carbon atoms, optionally substituted by one or more alkyl groups having from 1 to 4 carbon atoms or by hydroxy;

where 5. A compound as claimed in claim 1, in which R has the formula 6. A compound as claimed in claim I, in which R has the formula 7. A compound as claimed in claim 1, in which R has the formula 8. A compound as claimed in claim 1, in which R has the formula 9. A compound as claimed in claim 1, in which R has the formula --CH CH Q 10. A compound as claimed in claim 1, in which R has the formula 11. A compound as claimed in claim 1, in which R has the formula 12. A compound as claimed in claim 1, in which R has the formula 13. A compound as claimed in claim 1, in which R has the formula -CH endo 14. A compound as claimed in claim 1, in which R has the formula 15. A compound as claimed in claim 1, in which R has the formula action is carried out at temperatures from 20 to 40C. 

1. A TRIAZINO-BENZIMIDAZOLES OF THE FORMULA
 2. A compound as claimed in claim 1, having the formula
 3. A compound as claimed in claim 1, in which R has the formula
 4. A compound as claimed in claim 1, in which R has the formula
 5. A compound as claimed in claim 1, in which R has the formula
 6. A compound as claimed in claim 1, in which R has the formula
 7. A compound as claimed in claim 1, in which R has the formula
 8. A compound as claimed in claim 1, in which R has the formula
 9. A compound as claimed in claim 1, in which R has the formula
 10. A compound as claimed in claim 1, in which R has the formula
 11. A compound as claimed in claim 1, in which R has the formula
 12. A compound as claimed in claim 1, in which R has the formula
 13. A compound as claimed in claim 1, in which R has the formula
 14. A compound as claimed in claim 1, in which R has the formula
 15. A compound as claimed in claim 1, in which R has the formula -C14H29
 16. A process for the preparation of triazino-benzimidazoles of the formula as claimed in claim 1, which comprises reacting a molar quantity of 2-methoxycarbonylamino-benzimidazole dissolved in a moderately polar aprotic solvent with equimolar to doubly molar quantity of a primary amine H2N-R where R is as defined in claim 1, and with a 2- to 4-fold excess of formaldehyde at temperatures from 0* to 80*C.
 17. The process as defined in claim 16 where the solvent is a chlorine-substituted methane.
 18. The process as defined in Claim 16, where the reaction is carried out at temperatures from 20* to 40*C. 